CN103603055B - The finishing method, solar battery sheet and preparation method thereof of monocrystalline silicon piece - Google Patents
The finishing method, solar battery sheet and preparation method thereof of monocrystalline silicon piece Download PDFInfo
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Abstract
The invention discloses a kind of finishing method of monocrystalline silicon piece, solar battery sheet and preparation method thereof.This finishing method be the back side being used for making back surface field of the monocrystalline silicon piece after making herbs into wool is placed in polishing fluid, front is placed in outside polishing fluid and carries out chemical rightenning.By adding the planeness of silicon chip battery back surface field to back side suede structure polishing, add the reflection of solar spectrum medium-long wave band light at the silicon single crystal back side; Reduce the recombination rate of the matte area of silicon chip back side and the surface imperfection density of states(DOS) of silicon chip back side and back side photo-generated carrier, the light through silicon chip is made to be reflected back silicon chip inside more, add the probability that excitation electron-hole is right, improve the open circuit voltage of solar cell, short-circuit current and photoelectric transformation efficiency, reduce cost of manufacture.Improve long-wave band sun light reflectance by adjusting and optimizing glossing, make the light of long wavelength be reflected back silicon chip inside further and add absorbed possibility, improve the efficiency of conversion of solar cell.
Description
Technical field
The present invention relates to technical field of solar batteries, in particular to a kind of finishing method, solar battery sheet and preparation method thereof of monocrystalline silicon piece.
Background technology
Along with market competition is day by day fierce, the design and R&D of high performance solar batteries becomes the Main way of current researchdevelopment.The Making programme of current General N type monocrystaline silicon solar cell comprises silicon wafer wool making, P diffusion, wet etching, B diffusion, plasma etching, wet-chemical, antireflective coating deposition and the step such as silk screen printing and sintering.The back side of n type single crystal silicon utilizes P diffusion as the back surface field of solar cell, and therefore, how to be optimized adjustment to the back side of n type single crystal silicon battery is a kind of important channel of improving conversion efficiency of solar cell.
Current monocrystalline making herbs into wool is mainly groove type etching, be placed in texturing slot by silicon single crystal and soak the regular hour, tow sides at monocrystalline silicon piece after making herbs into wool all define " pyramid " matte, one side as solar cell back surface field then requires that silicon chip surface is smooth, the reflection of solar spectrum medium-long wave band spectrum at the n type single crystal silicon back side can be increased like this, the sunlight of long-wave band is made to be reflected back silicon chip inside, be conducive to the absorption and the conversion that increase long-wave band sunlight, and then improve the efficiency of conversion of solar cell.Therefore, glossing plays an important role in the research and development making solar cell and application.
At present to the polishing of silicon chip be generally to cutting after silicon chip adopt the thinning then nano-milled polishing of acid and alkali corrosion and have the operational path of wax polishing.And mechanical polishing is generally for the finishing method after making herbs into wool, and mechanical polishing is unfavorable for the scale operation of solar cell, also add production cost simultaneously.Therefore, how under the prerequisite reduced costs, planarizing process to be carried out to the silicon chip after making herbs into wool, and then increase silicon chip surface to sun light reflectance, become the focus of research at present.
Summary of the invention
The present invention aims to provide a kind of finishing method, solar battery sheet and preparation method thereof of monocrystalline silicon piece, increases cost and can not the problem brought of scale operation to solve in prior art to the silicon chip mechanical polishing after making herbs into wool.
To achieve these goals, according to an aspect of the present invention, provide a kind of finishing method of monocrystalline silicon piece, the back side being used for making back surface field of the monocrystalline silicon piece after making herbs into wool is placed in polishing fluid, front is placed in outside polishing fluid and carries out chemical rightenning.
Further, polishing fluid is the mixed solution of nitric acid and hydrofluoric acid.
Further, in polishing fluid, the volume ratio of nitric acid and hydrofluoric acid is 10:1 ~ 15:1, and the mass percent concentration of nitric acid is 55 ~ 75%, and the mass percent concentration of hydrofluoric acid is 30 ~ 50%, and polishing time is 3.77 ~ 5.48 minutes.
Further, in polishing fluid, the volume ratio of nitric acid and hydrofluoric acid is 12:1 ~ 14:1, and the mass percent concentration of nitric acid is 60 ~ 70%, and the mass percent concentration of hydrofluoric acid is 35 ~ 45%, and polishing time is 4.12 ~ 5.02 minutes.
Further, in polishing fluid, the volume ratio of nitric acid and hydrofluoric acid is 13:1, and the mass percent concentration of nitric acid is 65%, and the mass percent concentration of hydrofluoric acid is 40%, and polishing time is 4.54 minutes.
Further, the automatic makeup liquid measure of nitric acid is 0.2 ~ 0.6L/100 sheet, and the automatic makeup liquid measure of hydrofluoric acid is 0.1 ~ 0.3L/100 sheet.
According to a further aspect in the invention, provide a kind of making method of solar battery sheet, comprise the step to monocrystalline silicon piece polishing, polishing step adopts any one finishing method above-mentioned to implement.
According to another aspect of the invention, provide a kind of solar battery sheet, this solar battery sheet adopts any one making method above-mentioned to be made.
Apply technical scheme of the present invention, back side monocrystalline silicon piece after making herbs into wool being used for making back surface field is placed in polishing fluid, front is placed in polishing fluid and keep for some time outward, by carrying out polishing to the suede structure at the back side thus making solar cell back surface field on silicon chip more smooth, add the reflection of solar spectrum medium-long wave band spectrum at the silicon single crystal back side; Simultaneously owing to reducing the matte area of silicon chip back side, and then reduce the surface imperfection density of states(DOS) of silicon chip back side and the recombination rate of back side photo-generated carrier, make the light through silicon chip be reflected back silicon chip inside more and increase the right probability in excitation electron-hole, improve with the open circuit voltage of the solar cell of this silicon wafer to manufacture and short-circuit current on this basis, and then improve the photoelectric transformation efficiency of battery, reduce the cost of manufacture of battery unit.Visible, the present invention is by adjusting and optimizing the glossing of silicon single crystal back surface field and then improve long-wave band sun light reflectance, make the light of long wavelength be reflected back silicon chip inside further and increase absorbed possibility, thus improve the efficiency of conversion of solar cell, be suitable for suitability for industrialized production.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows internal quantum efficiency (IQE) schematic diagram of the solar cell of the silicon wafer to manufacture adopting glossing of the present invention and non-polished technique.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
Adopt the cost that causes of mechanical polishing high and cannot the problem of scale operation in order to solve in prior art to the monocrystalline silicon piece after making herbs into wool, the invention provides a kind of finishing method of monocrystalline silicon piece, the back side being used for making back surface field of the monocrystalline silicon piece after making herbs into wool is placed in polishing fluid, front is placed in outside polishing fluid and carries out chemical rightenning.
Back side monocrystalline silicon piece after making herbs into wool being used for making back surface field is placed in polishing fluid, front is placed in polishing fluid and keep for some time outward, by carrying out polishing to the suede structure at the back side thus making solar cell back surface field on silicon chip more smooth, add the reflection of solar spectrum medium-long wave band spectrum at the silicon single crystal back side; Simultaneously owing to reducing the matte area of silicon chip back side, and then reduce the surface imperfection density of states(DOS) of silicon chip back side and the recombination rate of back side photo-generated carrier, make the light through silicon chip be reflected back silicon chip inside more and increase the right probability in excitation electron-hole, improve with the open circuit voltage of the solar cell of this silicon wafer to manufacture and short-circuit current on this basis, and then improve the photoelectric transformation efficiency of battery, reduce the cost of manufacture of battery unit.Visible, the present invention is by adjusting and optimizing the glossing of silicon single crystal back surface field and then improve long-wave band sun light reflectance, make the light of long wavelength be reflected back silicon chip inside further and increase absorbed possibility, thus improve the efficiency of conversion of solar cell, be suitable for suitability for industrialized production.
Polishing fluid refers to that the matte after to silicon wafer wool making produces certain corrosive liquid, to ensure that and only carries out polishing to the back side that silicon chip is used for making back surface field, remaining the suede structure that front side of silicon wafer is complete by being placed in the front of silicon chip outside polishing liquid.Wherein adopted silicon chip can be silicon single crystal silicon chip and class silicon single crystal silicon chip, after making herbs into wool, the part of non-(100) crystal face of front side of silicon wafer is no longer luminous, reduce the difference with (100) crystal face, make silicon chip consistent to the reflecting effect of light in each position, improve with the serviceability of the solar cell of this silicon wafer to manufacture.But the silicon chip after making herbs into wool all defines " pyramid " matte at tow sides, the mode that the present invention adopts polishing fluid to corrode makes the back side as solar cell back surface field be corroded and then reaches the object of surfacing, thus increase the reflection of solar spectrum medium-long wave band spectrum at the n type single crystal silicon back side, the sunlight of long-wave band is made to be reflected back silicon chip inside, increase absorption and the conversion of long-wave band sunlight, and then improve the efficiency of conversion of solar cell.
Acid attack is isotropic etch, and " pyramid " structure matte after adopting acidic solution can make making herbs into wool becomes smooth.A preferred embodiment of the invention, polishing fluid is the mixed solution of nitric acid and hydrofluoric acid.After silicon chip back side after making herbs into wool is kept certain hour in the mixed solution of nitric acid and hydrofluoric acid, obtain flat appearance, consistence is good and aberration is less, reflectivity is high polished surface, improve the specific absorption of silicon chip to light and the photoelectric transformation efficiency of battery.In order to obtain better polished surface, improve the specific absorption of silicon chip to light largely, needing the mass percent concentration to nitric acid and hydrofluoric acid, volume mixture ratio and polishing time allocate and select.Preferably, in polishing fluid, the volume ratio of nitric acid and hydrofluoric acid is 10:1 ~ 15:1, and the mass percent concentration of nitric acid is 55 ~ 75%, and the mass percent concentration of hydrofluoric acid is 30 ~ 50%, and the time of polishing is 3.77 ~ 5.48 minutes.When adopting the mixture of the nitric acid of above-mentioned concentration range and volume ratio and hydrofluoric acid, then need polishing time to be limited in above-mentioned scope, if polishing time was lower than 3.77 minutes, the planeness of polished surface can be reduced because etching time is too short, if etching time was more than 5.48 minutes, then can because of the suede structure of the long destruction silicon chip surface of etching time.
Further preferably, in polishing fluid, the volume ratio of nitric acid and hydrofluoric acid is 12:1 ~ 14:1, and the mass percent concentration of nitric acid is 60 ~ 70%, and the mass percent concentration of hydrofluoric acid is 35 ~ 45%, and polishing time is 4.12 ~ 5.02 minutes.Most preferably, in polishing fluid, the volume ratio of nitric acid and hydrofluoric acid is 13:1, and the mass percent concentration of nitric acid is 65%, and the mass percent concentration of hydrofluoric acid is 40%, and polishing time is 4.54 minutes.
General employing chain type acid corrosion liquid carries out polishing, along with the prolongation of time in polishing process, nitric acid and hydrofluoric acid all have a certain amount of consumption, its concentration is also changing, in order to ensure polishing effect, need the mixed solution of nitric acid and hydrofluoric acid to control in certain concentration range, therefore, carrying out fluid infusion to nitric acid and hydrofluoric acid is a kind of efficient manner.Wherein the size of amount infused is weighed according to silicon slice corrosion quality, is referred to as automatic makeup liquid measure.Preferably, the automatic makeup liquid measure of nitric acid is 0.2 ~ 0.6L/100 sheet, and the automatic makeup liquid measure of hydrofluoric acid is 0.1 ~ 0.3L/100 sheet.
According to a further aspect in the invention, additionally provide a kind of making method of solar battery sheet, comprise the step to monocrystalline silicon piece polishing, wherein polishing step adopts any one finishing method above-mentioned to implement.
According to another aspect of the invention, provide a kind of solar battery sheet, this solar battery sheet adopts above-mentioned making method to be made.Adopt the solar battery sheet that above-mentioned making method obtains, the back side is more smooth, relatively reduce the matte area in solar cell back face, add the reflection of solar spectrum medium-long wave band spectrum at the silicon single crystal back side, because after polishing, the defect of silicon chip back side is less, higher to light reflectance, more light is made to go back to cell piece inside by backside reflection and then add the right probability in excitation electron-hole, the open circuit voltage of solar battery sheet and short-circuit current are improved on this basis, and then improve the photoelectric transformation efficiency of battery.
Below in conjunction with specific embodiment and comparative example, further illustrate beneficial effect of the present invention.
Embodiment 1
Surface preparation is carried out to the n type single crystal silicon sheet of 156 × 156, be placed in the groove type etching equipment filling sodium hydroxide solution (mass percent concentration is 5%), take out keep 480s at 75 DEG C after, obtain the silicon chip after alkali making herbs into wool.
Silicon chip after making herbs into wool is placed in the chain-type texture-etching equipment filling polishing fluid, this polishing fluid is HNO
3with the mixed solution of HF, wherein HNO
3be HNO with the volume ratio of HF
3: HF=13:1, the mass percent concentration of nitric acid is 65%, and the mass percent concentration of hydrofluoric acid is 40%.In utilize running roller to control polishing fluid that the above-mentioned nitric acid that swims in of silicon chip mixes with hydrofluoric acid, and the front of silicon chip is placed in outside polishing fluid, and the back side of silicon chip is placed in polishing fluid, at 12 DEG C, keep 60s, obtains silicon chip after polishing.
Embodiment 2 ~ 7
Its operation steps is identical with embodiment 1, and difference is HNO
3with the mass percent concentration of HF, volume ratio and polishing time, specifically in table 1.
Embodiment 8 ~ 9
Embodiment 7 is identical with embodiment 1 with the operation steps of embodiment 8, and difference is only to adopt HNO in embodiment 8
3as polishing fluid, only adopt in embodiment 9 HF as polishing fluid.
Comparative example 1
Polishing fluid is not adopted to carry out polishing in comparative example 1, but directly by diffusion after the silicon chip washing after making herbs into wool.
The design parameter condition of embodiment 1 to 9 and comparative example 1 is in table 1.
Table 1
The silicon chip produced in embodiment 1 to 9 and comparative example 1 is carried out under the same conditions successively P diffusion, wet etching, B diffusion, plasma etching, wet-chemical, antireflective coating deposition and silk screen printing and sintering, obtain corresponding solar battery sheet.Wherein adopt spectral response measurement instrument device to detect the internal quantum efficiency of the solar battery sheet in embodiment 1 and comparative example 1, its changes in contrast trend map is shown in Fig. 1.As can be seen from Figure 1, in embodiment 1 through the internal quantum efficiency of the latter made solar cell of polishing industrial treatment in the scope that wavelength is 975 ~ 1200nm compared with comparative example 1 in had raising to a certain degree without the internal quantum efficiency of the latter made solar cell of polished finish, finally make battery conversion efficiency improve about 0.10 ~ 0.25%.
Adopt halm testing tool to measure the open circuit voltage (Uoc) of solar battery sheet, short-circuit current (Isc), packing factor (FF) and photoelectric transformation efficiency Eff, specific performance data are in table 2.
Table 2
Data as can be seen from table 2, compared with not adopting the solar battery sheet of polishing fluid in comparative example 1, owing to adopting polishing fluid to carry out polishing to silicon chip back side in embodiment 1 to 9, the pyramidal pinnacle of a pagoda height formed due to making herbs into wool is overleaf made to reduce after polishing, whole pyramid becomes level and smooth, its open circuit voltage, short-circuit current, packing factor and photoelectric transformation efficiency all get a promotion, and chemical rightenning is not carried out to the silicon chip after making herbs into wool in comparative example 1, but directly by diffusion after the silicon chip washing after making herbs into wool, and then making solar battery sheet, can find out through contrast, open circuit voltage in comparative example 1, short-circuit current, packing factor and photoelectric transformation efficiency are all than poor in embodiment 1 to 9.
Compared with embodiment 1 to 7, only adopt nitric acid as polishing fluid in embodiment 8, only adopt hydrofluoric acid as polishing fluid in embodiment 9, the back surface field planeness of the solar battery sheet of the silicon wafer to manufacture in embodiment 8 and embodiment 9 is poor, although the reflection of solar spectrum medium-long wave band spectrum at the silicon single crystal back side also can be increased to a certain extent, but it has little effect, show that the lifting degree of the aspects such as open circuit voltage, short-circuit current, packing factor and photoelectric transformation efficiency is also very micro-.
Compared with embodiment 1 to 5, although also use the mixed solution of nitric acid and hydrofluoric acid as polishing fluid in embodiment 6 and embodiment 7, but due to nitric acid and the volume ratio of hydrofluoric acid and the matching effect problem of both concentration, polishing time and automatic makeup liquid measure, compared with the solar battery sheet of the silicon wafer to manufacture adopted in embodiment 1 to 5, the lifting degree of solar battery sheet in open circuit voltage, short-circuit current, packing factor and photoelectric transformation efficiency etc. obtained in embodiment 6 and embodiment 7 is relatively low.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a finishing method for monocrystalline silicon piece, is characterized in that, the back side being used for making back surface field of the described monocrystalline silicon piece after making herbs into wool is placed in polishing fluid, front is placed in outside described polishing fluid and carries out chemical rightenning; Described polishing fluid is the mixed solution of nitric acid and hydrofluoric acid; The volume ratio of nitric acid and described hydrofluoric acid described in described polishing fluid is 12:1 ~ 14:1, and the mass percent concentration of described nitric acid is 60 ~ 70%, and the mass percent concentration of described hydrofluoric acid is 35 ~ 45%, and polishing time is 4.12 ~ 5.02 minutes.
2. finishing method according to claim 1, it is characterized in that, the volume ratio of nitric acid and described hydrofluoric acid described in described polishing fluid is 13:1, and the mass percent concentration of described nitric acid is 65%, the mass percent concentration of described hydrofluoric acid is 40%, and polishing time is 4.54 minutes.
3. finishing method according to claim 1, is characterized in that, the automatic makeup liquid measure of described nitric acid is 0.2 ~ 0.6L/100 sheet, and the automatic makeup liquid measure of described hydrofluoric acid is 0.1 ~ 0.3L/100 sheet.
4. a making method for solar battery sheet, comprises the step to monocrystalline silicon piece polishing, it is characterized in that, described polishing step adopts the finishing method according to any one of claims 1 to 3 to implement.
5. a solar battery sheet, is characterized in that, described solar battery sheet adopts making method according to claim 4 to be made.
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| CN104993019A (en) * | 2015-07-09 | 2015-10-21 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of localized back contact solar cell |
| CN105385359B (en) * | 2015-12-17 | 2018-07-13 | 常州时创能源科技有限公司 | The additive of crystalline silicon acid polishing slurry and its application |
| CN105696083B (en) * | 2016-01-29 | 2018-03-09 | 盐城阿特斯协鑫阳光电力科技有限公司 | A kind of preparation method of solar battery pile face |
| CN106653948A (en) * | 2016-12-28 | 2017-05-10 | 江西瑞晶太阳能科技有限公司 | Solar cell and cell back polishing process thereof |
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| CN102021657A (en) * | 2010-12-10 | 2011-04-20 | 天津中环领先材料技术有限公司 | Corrosion process for heavily doped monocrystalline silicon wafers sequentially subjected to acid corrosion and alkaline corrosion |
| CN102569502A (en) * | 2011-12-16 | 2012-07-11 | 合肥晶澳太阳能科技有限公司 | Wet method etching process |
| CN103205800A (en) * | 2012-01-17 | 2013-07-17 | 江苏协鑫硅材料科技发展有限公司 | Method for improving cast monocrystalline silicon ingot yield and conversion rate |
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| CN102021657A (en) * | 2010-12-10 | 2011-04-20 | 天津中环领先材料技术有限公司 | Corrosion process for heavily doped monocrystalline silicon wafers sequentially subjected to acid corrosion and alkaline corrosion |
| CN102569502A (en) * | 2011-12-16 | 2012-07-11 | 合肥晶澳太阳能科技有限公司 | Wet method etching process |
| CN103205800A (en) * | 2012-01-17 | 2013-07-17 | 江苏协鑫硅材料科技发展有限公司 | Method for improving cast monocrystalline silicon ingot yield and conversion rate |
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